Quantum chemical study on influence of intermolecular hydrogen bonding on the geometry, the atomic charges and the vibrational dynamics of 2,6-dichlorobenzonitrile

FT-IR (4000-400 cm(-1)) and FT-Raman (4000-200 cm(-1)) spectral measurements on solid 2,6-dichlorobenzonitrile (2,6-DCBN) have been done. The molecular geometry, harmonic vibrational frequencies and bonding features in the ground state have been calculated by density functional theory at the B3LYP/6-311++G (d,p) level. A comparison between the calculated and the experimental results covering the molecular structure has been made. The assignments of the fundamental vibrational modes have been done on the basis of the potential energy distribution (PED). To investigate the influence of intermolecular hydrogen bonding on the geometry, the charge distribution and the vibrational spectrum of 2,6-DCBN; calculations have been done for the monomer as well as the tetramer. The intermolecular interaction energies corrected for basis set superposition error (BSSE) have been calculated using counterpoise method. Based on these results, the correlations between the vibrational modes and the structure of the tetramer have been discussed. Molecular electrostatic potential (MEP) contour map has been plotted in order to predict how different geometries could interact. The Natural Bond Orbital (NBO) analysis has been done for the chemical interpretation of hyperconjugative interactions and electron density transfer between occupied (bonding or lone pair) orbitals to unoccupied (antibonding or Rydberg) orbitals. UV spectrum was measured in methanol solution. The energies and oscillator strengths were calculated by Time Dependent Density Functional Theory (TD-DFT) and matched to the experimental findings. TD-DFT method has also been used for theoretically studying the hydrogen bonding dynamics by monitoring the spectral shifts of some characteristic vibrational modes involved in the formation of hydrogen bonds in the ground and the first excited state. The C-13 nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge independent atomic orbital (GIAO) method and compared with experimental results. Standard thermodynamic functions have been obtained and changes in thermodynamic properties on going from monomer to tetramer have been presented. (C) 2013 Elsevier B.V. All rights reserved.

Effects of CO2 enrichment on the bloom-forming cyanobacterium Microcystis aeruginosa (Cyanophyceae): Physiological responses and relationships with the availability of dissolved inorganic carbon

Microcystis aeruginosa Kutz. 7820 was cultured at 350 and 700 muL.L-1 CO2 to assess the impacts of doubled atmospheric CO2 concentration on this bloom-forming cyanobacterium. Doubling Of CO2 concentration in the airflow enhanced its growth by 52%-77%, with pH values decreased and dissolved inorganic carbon (DIC) increased in the medium. Photosynthetic efficiencies and dark respiratory rates expressed per unit chl a tended to increase with the doubling of CO2. However, saturating irradiances for photosynthesis and light-saturated photosynthetic rates normalized to cell number tended to decrease with the increase of DIC in the medium. Doubling of CO2 concentration in the airflow had less effect on DIC-saturated photosynthetic rates and apparent photosynthetic affinities for DIC. In the exponential phase, CO2 and HCO3- levels in the medium were higher than those required to saturate photosynthesis. Cultures with surface aeration were DIC limited in the stationary phase. The rate of CO2 dissolution into the liquid increased proportionally when CO2 in air was raised from 350 to 700 muL.L-1, thus increasing the availability of DIC in the medium and enhancing the rate of photosynthesis. Doubled CO2 could enhance CO2 dissolution, lower pH values, and influence the ionization fractions of various DIC species even when the photosynthesis was not DIC limited. Consequently, HCO3- concentrations in cultures were significantly higher than in controls, and the photosynthetic energy cost for the operation of CO2 concentrating mechanism might decrease.

Impact of hydrogen dilution on microstructure and optoelectronic properties of silicon films deposited using tirisilane

We explored the deposition of hydrogenated amorphous silicon (a-Si: H) using trisilane (Si3H8) as a gas precursor in a radiofrequency plasma enhanced chemical vapour deposition process and studied the suitability of this material for photovoltaic applications. The impact of hydrogen dilution on the deposition rate and microstructure of the films is systematically examined. Materials deposited using trisilane are compared with that using disilane (Si2H6). It is found that when using Si3H8 as the gas precursor the deposition rate increases by a factor of similar to 1.5 for the same hydrogen dilution (R = [H-2]/[Si3H8] or [H-2]/[Si2H6])- Moreover, the structural transition from amorphous to nanocrystalline occurs at a higher hydrogen dilution level for Si3H8 and the transition is more gradual as compared with Si2H6 deposited films. Single-junction n-i-p a-Si: H solar cells were prepared with intrinsic layers deposited using Si3H8 or Si2H6. The dependence of open circuit voltage (V-oc) on hydrogen dilution was investigated. V-oc greater than 1 V can be obtained when the i-layers are deposited at a hydrogen dilution of 180 and 100 using Si3H8 and Si2H6, respectively.

Cooperative spontaneous emission of excitons in the semiconductor microcavity

We have studied the spontaneous emission of polarized excitons in the GaInP/AlGaInP VCSEL from 30K to room temperature. It is observed that the spontaneous emission peak enters and leaves the resonant regime. At the resonant regime, the emission intensities of the perpendicular and horizontal polarized exciton are enhanced at different ratio to those in non-resonant regime. These experiment results are explained through the dressed exciton theory of the semiconductor microcavity device. From this theory, the intensity enhancement and the polarization dependence are understood as cooperative emission and the microcavity anisotropy.

Gas-phase isothermal chromatography with short-lived technetium isotopes

In order to study the gas-phase chemical behavior of transactinides, an on-line isothermal chromatography apparatus has been developed and applied to separate short-lived technetium isotopes in the form of TcO3 from fission products. The fission products from a Cf-252 source were continuously and rapidly transported through the capillary to the isothermal chromatography apparatus using the N-2/KBr gas-jet techniques. Volatile oxide molecules were formed at the reaction zone kept at 900 degrees C since a trace amount of oxygen existed in the N-2 carrier gas. With the new developed isothermal chromatography apparatus, a selective separation of Tc from fission products was achieved. After isothermal chromatographic separation, Tc-101,Tc-103,Tc-104,Tc-105,Tc-106,Tc-107,Tc-108 were dominantly observed together with their Ru daughters in the gamma-spectrum, The chemical yields of Tc-101, and Tc-104 and Tc-105 isotopes with longer half-lives are about 55-57%, and those of Tc-103, Tc-106 and Tc-108 isotopes with shorter half-lives dropped down to 25-28%. The adsorption enthalpy of the investigated compounds on quartz surfaces was determined to be -150 +/- 5 kJ/mol by fitting the measured retention curves with a Monte Carlo model. The observed species of technetium oxide is attributed to TcO3, which is in good agreement with previous experimental results. That means our system worked properly and it can be used to investigate the gas-phase chemical behavior of transactinides.

Analysis of aromatic amines by high-performance liquid chromatography with pre-column derivatization by 2-(9-carbazole)-ethyl-chloroformate

2-(9-Carbazole)-ethyl-chloroformate (CEOC), a novel pre-column fluorescence derivatization reagent, has been developed for the analysis of aromatic amines. Taking five monocyclic aromatic amines (o-toluidine, aniline, 3,4-dimethylaniline, N-ethyl-p-toluidine, and p-phenylenediamine) as testing compounds, derivatization conditions such as pH of borate buffer, reaction time and fluorescent tagging reagent concentration have been investigated. By a one-step procedure, CEOC reacts readily with the aromatic amines to form stable derivatives with excitation and emission wavelengths, respectively, at 293 and 360 nm. This derivatization reaction could be finished within 20 min even at room temperature. The peak shapes of the derivatized aromatic amines can be improved greatly without any addition of competition amines into the mobile phase. Furthermore, this method can offer excellent quantitative precision with high tolerance of the matrix of samples. (C) 2003 Elsevier B.V. All rights reserved.

A Comparison of the Contribution of Various Gases to the Greenhouse Effect

The current concern about an anthropogenic impact on global climate has made it of interest to compare the potential effect of various human activities. A case in point is the comparison between the emission of greenhouse gases from the use of natural gas and that from other fossil fuels. This comparison requires an evaluation of the effect of methane emissions relative to that of carbon dioxide emissions. A rough analysis based on the use of currently accepted values shows that natural gas is preferable to other fossil fuels in consideration of the greenhouse effect as long as its leakage can be limited to 3 to 6 percent.

Preparation and characterization of La2Zr2O7 coating with the addition of Y2O3 by EB-PVD

Thermal barrier coatings (TBCs) of La2Zr2O7 (LZ) with the addition of 3 wt.% Y2O3 (LZ3Y) were deposited by electron beam-physical vapor deposition (EB-PVD). The phase stabilities, thermophysical and mechanical properties, and chemical compositions of these ceramics and coatings were studied in detail. The phase stability and thermal expansion behavior of LZ3Y bulk material are identical to those of LZ bulk material, but the mechanical properties of the former are superior to those of the latter. Elemental analysis and X-ray diffraction indicate that compositional deviation of LZ coating can be optimized after doping by 3 wt.% Y2O3, Y2O3 acts as a dopant as well as a process regulator. The optimal composition of LZ3Y coating could be effectively achieved by the addition of excess Y2O3 into the ingot and by properly controlling the current of electron beam (i.e. similar to 650 mA).

Advances in gas-phase electrophilic aromatic substitution reaction

Recent advances in the gas - phase reaction of aromatics with cationic electrophiles are reviewed. The overall substitution reaction is analyzed in terms of its elementary steps. Mechanistic studies have been focused on the structure and reactivity of covalent and non - covalent ionic intermediates, which display a rich chemistry and provide benchmark reactivity models. Particular attention has been devoted to proton transfer reactions, which may occur intra or intermolecularly in arenium intermediates.

Mass spectrometric studies of metallofullerene

The endrohel metallofullerene, Gd@C-82, Gd@C-80, Gd-2@C-80 were synthesized by using K-H method. The technique of two-step of high pressure and high temperature extraction with 1, 3, 5-trimethylbenzene (first step) and pyridine(second step) has been successfully utilized to extract metallofullerene of Gd@C-82 The gas-phase negative ions of fullerenes C-n(n= 60, 70, 78, 82, 84...) and metallofullerene (Gd@C-82) have been studied by the ESI-MS, REC-MS and MALDI-TOF-MS. The differences among the mass spectra of ESI-MS, REC-MS and MALDI-TOF-MS have been observed and explained. In contrast to the empty fullerene C-82 , the metallofullerene Gd@C-82 should have a larger HOMO-LUMO gap. Experimental results suggest that Gd@C-82 is polarized and Gd3+ located in the off-center position of C-82 cage after Gd3+ is trapped into C-82 cage.

Studies on blends of LLDPE and ethylene-methacrylic acid random copolymer

Blends of linear low-density polyethylene (LLDPE) and poly(ethylene-co-methacrylic acid) (EMA) random copolymer were studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and excimer fluorescence. In binary blends, crystallization of EMA was studied, and no modification of crystal structure was detected. In excimer fluorescence measurements, emission intensities of blends of EMA and naphthalene-labeled LLDPE were measured. The ratio of the excimer emission intensity (I-D) to the emission intensity of the isolated "monomer" (I-M) decreases upon addition of EMA, indicating that PE segments of EMA interpenetrate into the amorphous phase of LLDPE. (C) 1998 Published by Elsevier Science Ltd,. All rights reserved.

General expression for probabilistic estimation of multiphase structure invariants in the case of a native protein and multiple derivatives. Application to estimates of the three-phase structure invariants

Concise probabilistic formulae with definite crystallographic implications are obtained from the distribution for eight three-phase structure invariants (3PSIs) in the case of a native protein and a heavy-atom derivative [Hauptman (1982). Acta Cryst. A38, 289-294] and from the distribution for 27 3PSIs in the case of a native and two derivatives [Fortier, Weeks & Hauptman (1984). Acta Cryst. A40, 646-651]. The main results of the probabilistic formulae for the four-phase structure invariants are presented and compared with those for the 3PSIs. The analysis directly leads to a general formula of probabilistic estimation for the n-phase structure invariants in the case of a native and m derivatives. The factors affecting the estimated accuracy of the 3PSIs are examined using the diffraction data from a moderate-sized protein. A method to estimate a set of the large-modulus invariants, each corresponding to one of the eight 3PSIs, that has the largest \Delta\ values and relatively large structure-factor moduli between the native and derivative is suggested, which remarkably improves the accuracy, and thus a phasing procedure making full use of all eight 3PSIs is proposed.

Electron-impact ionization of hydrogen-like iron ions

Electron-impact ionization cross sections have been determined for hydrogen like iron ions at selected electron energies between 1.45 and 4.3 times the threshold energy. The cross sections were obtained by measuring the equilibrium ionization balance in an electron beam ion trap. This ionization balance is obtained from x-ray measurements of radiative recombination into the K-shell of hydrogen-like and bare iron ions. The measured cross sections are compared with distorted-wave calculations and several semiempirical formulations.

An investigation into the behaviour of concrete containing seawater-neutralised bauxite refinery residues in silage effluent

The farm production of silage as a winter-feed supplement is widespread. However, the bins in which silage is produced are subject to acidic and microbial attacks. Both these types of attack can lead to a weakening and failure of the concretes, especially on the outer lip of the open side of the silage pit. Consequently, the development of an acid-resistant concrete that can extend the life span of silage bins on farms could lead to considerable cost savings for farmers and, hence, can improve farm productivity. This paper reports on test results of an investigation into the behaviour of concrete containing seawater-neutralised bauxite refinery residues (Bauxsol™) exposed to sulphuric acid environments in the laboratory and to silage effluents. The concrete manufactured had a fixed water–cement ratio of 0.55 and natural sand was replaced with the Bauxsol™ at 0%, 5%, 10%, 15% and 20% by cement mass. Results indicated that the use of Bauxsol™ as a sand replacement material improved the behaviour of concrete both in sulphuric acid in the laboratory as well as in the silage effluent. Consequently, it is concluded that the Bauxsol™ can be used to replace 10% of natural sand to produce concrete that is resistant to silage effluents, providing an extended service life over conventional concretes used in silage pits.